US6011191A - Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene - Google Patents

Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene Download PDF

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US6011191A
US6011191A US09/079,292 US7929298A US6011191A US 6011191 A US6011191 A US 6011191A US 7929298 A US7929298 A US 7929298A US 6011191 A US6011191 A US 6011191A
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isobutene
process according
primary alcohols
alkyl ethers
weight
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Marco Di Girolamo
Lorenzo Tagliabue
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SnamProgetti SpA
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Assigned to SNAMPROGETTI S.P.A. reassignment SNAMPROGETTI S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DI GIROLAMO, MARCO, TAGLIABUE, LORENZO
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation

Definitions

  • the present invention relates to a process for the production of hydrocarbons with a high octane number, obtained by the selective dimerization reaction of isobutene contained in hydrocarbon cute and to a lesser extent of possible linear butanes, in the presence of moderate quantities of primary alcohols and alkyl ethers, which favour the production of higher selectivities on the part of the catalyst.
  • the mixture obtained can then be hydrogenated with the conventional methods to obtain a product with a further improvement in the octane characteristics.
  • CAAA Carrier Air Act Amendments
  • oxygenated compounds will have an ever increasing role as fuel components
  • the alkylation process in liquid phase is a reaction between isoparaffinic hydrocarbons, such as for example, isobutane, and olefins, for example propylene, butenes, pentenes and relative mixtures, in the presence of an acid catalyst for the production of C 7 -C 9 hydrocarbons with a high octane number to be used in fuels (see for example: A. Corma, A. Martinez, Catal. Rev.- Sci. Eng., 35, (1993), 483 and references contained therein).
  • hydrocarbon product of this type is in ever-increasing demand owing to its octane characteristics (high Research Octane Number (RON) and Motor Octane Number (MON) and those relating to its boiling point (poor volatility but low final point) which place it in the category of compositions which are extremely interesting for obtaining fuels that are more compatible with present-day environmental demands.
  • RON Research Octane Number
  • MON Motor Octane Number
  • hydrocarbon products with a high octane number such as those generated by the alkylation reaction also have a low sensitivity (difference between RON and MON) and it is known that ethers such as MTBE, ETBE, TAME, etc. favourably react to the reduced sensitivity of the fuel, increasing their already high octane number even more.
  • the oligomerization process (often erroneously called, in the field of refining, polymerization) was widely used in the years 1930-1940 to convert low-boiling C 3 -C 4 olefins into fuels.
  • the process leads to the production of a fuel with a high octane number (RON about 97) but with a high Sensitivity owing to the purely olefinic nature of the product (for more specific details on the process see: J. H. Gary, G. E. Stress, "Petroloum Refining: Technology and Economics", 3rd Ed., M. Dekker, New York, (1994), 250).
  • Typical olefins which are oligomerized are mainly propylene, which gives slightly higher dimers or oligomers depending on the process used, and isobutene which mainly gives dimers but always accompanied by large quantities of higher oligomers.
  • Typical catalysts for the industrial oligomerization of isobutene are represented by phosphoric acid, generally supported on a solid (for example kieselguhr), or acid resins with cation exchange.
  • a solid for example kieselguhr
  • acid resins with cation exchange The latter allow blander conditions of both temperature and pressure to be used than with supported phosphoric acid (100° C. and 1-2 Mpa vs 200-220° C. and 3-10 MPa).
  • the main problem of this process lies in the fact that in the oligomerization phase heavy oligomers such as trimers (selectivity of 15-30%) and tetramers (selectivity of 1-2%) of isobutene are produced in excessive percentages. Tetramers are completely outside the fuel fraction as they are too high-boiling and therefore represent a distinct loss in fuel yield; with respect to trimers (or their hydrogenated derivatives) it is desirable to strongly reduce their concentration as their boiling point (170-180° C.) is on the limit of future specifications on the final point of reformulated fuels
  • This level of heavy compounds is analogous to that of an alkylate and is still tolerated in the fuel pool.
  • the reaction product is then preferably hydrogenated to give a completely saturated end-product with a high octane number and low sensitivity.
  • the hydrogenation can be carried out with the conventional methods as described for example in F.Asinger, "Mono-olefins: Chemistry and Technology", Pergamon Press, Oxford, page 455.
  • table I indicates the octane numbers and relative boiling points of some of the products obtained with the process of the present invention.
  • the process of the present invention for the production of hydrocarbons with a high octane number starting from hydrocarbon cuts containing isobutene, by selective dimerization with acid catalysts is characterized in that the reaction in carried out in the presence of primary alcohols in such a quantity as to have in the feeding a molar ratio primary alcohols+alkyl ethers/isobutene of more than 0.1, preferably between 0.1 and 0.7, and a ratio primary alcohol/isobutene of less than 0.2, preferably between 0.005 and 0.1.
  • the process claimed herein can be applied to cuts containing isobutane, isobutene, n-butane and n-butenes.
  • the stream comprises as specified above, primary alcohol (in great molar defect with respect to the iso-olefin) and alkyl ether.
  • the primary alcohol used can be selected from primary alcohols containing from 1 to 6 carbon atoms: methanol and/or ethanol are preferred.
  • the alkyl ether used can be selected from those containing from 5 to 10 carbon atoms: MTBE (methyl-ter-butyl ether), ETBE (ethyl-ter-butyl ether), MSBE (methyl-sec-butyl ether), ESBE (ethyl-sec-butyl ether) or mixtures of these are preferred.
  • the isobutene together with the hydrocarbon stream in which it is contained is sent with the primary alcohol and alkyl ether, in strong stoichiometric defect, into contact with the acid catalyst where the dimerization takes place.
  • the primary alcohol is almost completely converted under the reaction conditions to dimer ether.
  • the quantity of alkyl ether sent to the reactors is such that, depending on the operating conditions, it can be either further produced or partially decomposed: in the latter case, as the decomposition process is of endothermal ether, a part of the heat developed in the dimerization reaction can be absorbed, thus further improving the temperature control in the reactor.
  • the alcohol liberated by the decomposition of the ether, as well as interacting with the catalyst can react with the dimers and butenes present in the reactor.
  • the charge consists of C 4 hydrocarbon cuts containing isobutene in a quantity of between 30 and 60% by weight, n-butenes in a quantity of more than 30% by weight and C 4 paraffins in a quantity of less than 15% by weight, it is advisable, to obtain better results, to operate with a molar ratio primary alcohol+alkyl ether/isobutene of between 0.1 and 0.6.
  • the charge consists of C 4 hydrocarbon cuts containing isobutene in a quantity of between 28 and 60% by weight, C 4 paraffins in a quantity of more than 30% by weight and n-butenes in a quantity of less than 10% by weight, it is advisable, to obtain better results, to operate with a molar ratio primary alcohol+alkyl ether/isobutene of between 0.3 and 0.6.
  • Table II indicates the average compositions of typical C 4 hydrocarbon fractions coming from different sources (FCC, Steam Cracking, dehydrogenation of isobutane, streams of isobutene with a high concentration).
  • a wide variety of acid catalysts can be used for this process, among these, for example, mineral acids such as sulfuric acid, BF 3 , supported phosphoric acid, suitably modified zeolites, heteropolyacids and sulfonated polymeric resins, for example Amberlyst 15 and Amberlyst 35, etc, can be mentioned.
  • mineral acids such as sulfuric acid, BF 3
  • supported phosphoric acid suitably modified zeolites, heteropolyacids and sulfonated polymeric resins, for example Amberlyst 15 and Amberlyst 35, etc
  • macrolattice sulfonated resins generally copolymers of styrene and benzene
  • characteristics of these resins are amply described in literature (see for example A. Mitschker, R.Wagner, P. M. Lange, "Heterogeneous Catalysis and Fine Chemicals", M. Cuisnet ed., Elsevier, Amsterdam (1988), 61).
  • a wide range of operating conditions can be used for producing hydrocarbons with a high octane number in the desired selectivities by the process of the present invention. It is possible to operate in vapor phase or in liquid-vapor phase but the operation conditions in liquid phase are preferred.
  • the process of the present invention can operate under both batch and continuous conditions, considering however that the latter are much more advantageous in industrial practice.
  • the reactor configuration selected can be optionally selected from fixed bed, tubular fixed bed, adiabatic, stirred and finally column reactor which also allows the separation of the products (a description on the general use of this technology is provided for example in: J. L. De Carmo, V. N. Paruledar, V. Pinjala, Chem. Eng. Progr., March 1992, 43).
  • the pressure in preferably superatmospheric to maintain the reagents in liquid phase, generally below 5 MPa, more preferably between 0.2-2.5 MPa.
  • the reaction temperature is preferably between 30 and 120° C.
  • the feeding space velocities of the alcohol-hydrocarbon stream should preferably be less than 30 h -1 , more preferably between 1 and 15 h -1 .
  • the isobutene is mainly converted in the reaction zone, however also part of the n-olefins can be converted to useful product; for the most part, there are no limits in the concentration of iso-olefin in the hydrocarbon fraction even if it is preferable to have concentrations of between 2 and 60%, there are no limits in the ratio between isobutene and linear olefins. It should be observed that in the case of streams coming from the dehydrogenation of isobutane there are no significant concentrations of linear butenes in the charge.
  • the effluent (4) from the reactor (A) is sent to a separation column (B) where a stream (6) is removed at the head, essentially containing non-converted olefins, alkyl ether (MTBE) and alcohol (methanol) in such quantities an to satisfy the molar ratios specified above, whereas at the bottom a stream (5) is removed essentially containing dimers, oligomers, ethers of dimers and alkyl ether (MTBE).
  • This stream (5) is sent to a separation column (C) where a stream is removed at the head, essentially containing alkyl ether (MTBE) recycled to the reactor (A), whereas at the bottom the synthesis product is obtained essentially consisting of dimers and small quantities of oligomers and ethers of dimers.
  • C separation column
  • the stream (6) is fed to a second reactor (D) in which the isobutene present is selectively converted to dimers.
  • the effluent (10) from the reactor (D) is separated in a column (E) from which a bottom stream (11) is removed, essentially containing alkyl ether (MTSE) and dimers, which is sent, together with the stream (5), to the column (C).
  • MTSE alkyl ether
  • the stream (12) at the head can be treated to remove the alcohol (methanol) contained therein in a unit (F) which can consist for example of an absorption system of the primary alcohol on molecular sieves or an extraction of the alcohol itself with water.
  • a unit (F) which can consist for example of an absorption system of the primary alcohol on molecular sieves or an extraction of the alcohol itself with water.
  • the alcohol recovered can be sent (14) to the reaction, whereas the hydrocarbon stream (13) can be used in subsequent operations.
  • a hydrocarbon stream containing 50% by weight of isobutene, of the type obtained by the dehydrogenation of isobutane is converted in the presence of suitable quantities of methanol and MTBE into a hydrocarbon product with a high octane number containing about 90% by weight of di-isobutenes, the rest consisting of trimers of isobutenes and ethers of di-isobutenes.
  • Tables XII and IV show with reference to the enclosed FIGURE, the quantities of the various streams of the plant indicated in kg/h, % weight, Kmol/h and % mol.
  • the reactors (A) and (D) operate at a temperature at the outlet of 70° C. and 75° C. respectively and both at an operating pressure of 2 MPa.
  • the molar ratio methanol+MTBE/isobutene is 0.375 in reactor (A) and 0.154 in reactor (B).
  • the catalyst used is a commercial macroporous sulfonated resin of the typo Amerlyst 35 produced by Rohm & Haas, Co.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US09/079,292 1997-05-15 1998-05-15 Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene Expired - Lifetime US6011191A (en)

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IT97MI001129A IT1291729B1 (it) 1997-05-15 1997-05-15 Procedimento per la produzione di idrocarburi altoottanici mediante dimerizzazione selettiva di isobutene
ITMI97A1129 1997-05-15

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6433238B1 (en) 1999-08-05 2002-08-13 Snamprogetti S.P.A. Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene
US6500999B2 (en) * 2000-05-26 2002-12-31 Snamprogetti S.P.A. Process for the production of hydrocarbons with a high octane number by means of the selective dimerization of isobutene with acid catalysts
US6613108B1 (en) * 1998-10-16 2003-09-02 Fortum Oil & Gas Oy Process for producing a fuel component
US20040020758A1 (en) * 2002-07-25 2004-02-05 Catalytic Distillation Technologies Separation of tertiary butyl alcohol from diisobutylene
US20050077211A1 (en) * 2003-10-10 2005-04-14 Snamprogetti S.P. A. Process for the production of hydrocarbon blends with a high octane number by the hydrogenation of hydrocarbon blends containing branched olefinic cuts
US20060065574A1 (en) * 2004-09-28 2006-03-30 Fortum Oil Oy Production of fuel components
US20060135832A1 (en) * 2004-12-16 2006-06-22 Vora Bipin V Process and apparatus for oligomerization in multiple stages with single fractionation column
WO2007057151A3 (en) * 2005-11-17 2007-07-26 Snam Progetti Process for the separation of c5 hydrocarbons present in streams prevalently containing c4 products used for the production of high-octane hydrocarbon compounds by the se- lective dimerization of isobutene
US20080164139A1 (en) * 2007-01-08 2008-07-10 Catalytic Distillation Technologies Treatment of olefin feed to paraffin alkylation
US20080242909A1 (en) * 2005-11-17 2008-10-02 Snamprogetti S.P.A. Process for the Production of High-Octane Hydrocarbon Compounds by the Selective Dimerization of Isobutene Contained in a Stream Which Also Contains C5 Hydrocarbons
US20100137668A1 (en) * 2008-12-02 2010-06-03 Catalytic Distillation Technologies Oligomerization process
EP2522424A1 (en) 2011-05-09 2012-11-14 King Abdulaziz City for Science and Technology Supported nanocatalyst for conversion of monoolefins, process for conversion of monoolefins and process for preparing the nanocatalyst
US20140012054A1 (en) * 2012-07-06 2014-01-09 Exxonmobil Chem Patents Inc Hydrocarbon Conversion Process

Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
ES2222678T3 (es) * 1998-10-16 2005-02-01 Fortum Oil And Gas Oy Proceso para la produccion de un componente de combustible.
US6660898B1 (en) 2000-11-03 2003-12-09 Fortum Oil & Gas Oy Process for dimerizing light olefins to produce a fuel component
EP1388528B1 (de) 2002-08-06 2015-04-08 Evonik Degussa GmbH Verfahren zur Oligomerisierung von Isobuten in n-Buten-haltigen Kohlenwasserstoffströmen
GB0307758D0 (en) * 2003-04-03 2003-05-07 Bp Chem Int Ltd Process
DE602004021819D1 (de) 2003-09-18 2009-08-13 Neste Oil Oyj Verfahren zur katalytischen desoxygenierung von verfahrensflüssigkeiten aus olefindimerisierungsverfahren
US8124819B2 (en) * 2009-01-08 2012-02-28 Catalytic Distillation Technologies Oligomerization process
IT1392673B1 (it) 2009-01-13 2012-03-16 Saipem Spa Procedimento per l'ottenimento di 1-butene ad elevata purezza da miscele idrocarburiche c4
FR2983090A1 (fr) 2011-11-30 2013-05-31 IFP Energies Nouvelles Composition catalytique contenant une fonction acide et procede pour la dimerisation selective de l'isobutene
FR2983091B1 (fr) 2011-11-30 2013-11-08 IFP Energies Nouvelles Composition catalytique et procede pour la dimerisation selective de l'isobutene

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US4100220A (en) * 1977-06-27 1978-07-11 Petro-Tex Chemical Corporation Dimerization of isobutene
US4447668A (en) * 1982-03-29 1984-05-08 Chemical Research & Licensing Company Process for producing high purity isoolefins and dimers thereof by dissociation of ethers
EP0467345A2 (en) * 1990-07-19 1992-01-22 Albemarle Corporation Olefine oligomerization process and products and use of dimer products
EP0745576A1 (en) * 1995-06-01 1996-12-04 SNAMPROGETTI S.p.A. Process for the joint production of ethers and hydrocarbons with a high octane number

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US4100220A (en) * 1977-06-27 1978-07-11 Petro-Tex Chemical Corporation Dimerization of isobutene
US4447668A (en) * 1982-03-29 1984-05-08 Chemical Research & Licensing Company Process for producing high purity isoolefins and dimers thereof by dissociation of ethers
EP0467345A2 (en) * 1990-07-19 1992-01-22 Albemarle Corporation Olefine oligomerization process and products and use of dimer products
EP0745576A1 (en) * 1995-06-01 1996-12-04 SNAMPROGETTI S.p.A. Process for the joint production of ethers and hydrocarbons with a high octane number

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6613108B1 (en) * 1998-10-16 2003-09-02 Fortum Oil & Gas Oy Process for producing a fuel component
US6433238B1 (en) 1999-08-05 2002-08-13 Snamprogetti S.P.A. Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene
US6500999B2 (en) * 2000-05-26 2002-12-31 Snamprogetti S.P.A. Process for the production of hydrocarbons with a high octane number by means of the selective dimerization of isobutene with acid catalysts
US20040020758A1 (en) * 2002-07-25 2004-02-05 Catalytic Distillation Technologies Separation of tertiary butyl alcohol from diisobutylene
US6863778B2 (en) 2002-07-25 2005-03-08 Catalytic Distillation Technologies Separation of tertiary butyl alcohol from diisobutylene
WO2004052808A3 (en) * 2002-12-09 2005-03-10 Catalytic Distillation Tech Separation of tertiary butyl alcohol from diisobutylene
US20050077211A1 (en) * 2003-10-10 2005-04-14 Snamprogetti S.P. A. Process for the production of hydrocarbon blends with a high octane number by the hydrogenation of hydrocarbon blends containing branched olefinic cuts
US7510646B2 (en) * 2003-10-10 2009-03-31 Snamprogetti S.P.A. Process for the production of hydrocarbon blends with a high octane number by the hydrogenation of hydrocarbon blends containing branched olefinic cuts
US20060065574A1 (en) * 2004-09-28 2006-03-30 Fortum Oil Oy Production of fuel components
US7344632B2 (en) 2004-09-28 2008-03-18 Neste Oil Oyj Production of fuel components
US20060135832A1 (en) * 2004-12-16 2006-06-22 Vora Bipin V Process and apparatus for oligomerization in multiple stages with single fractionation column
US8052945B2 (en) 2004-12-16 2011-11-08 Uop Llc Apparatus for oligomerization in multiple stages with single fractionation column
US20100316536A1 (en) * 2004-12-16 2010-12-16 Uop Llc Process and Apparatus for Oligomerization in Multiple Stages with Single Fractionation Column
US7803978B2 (en) 2004-12-16 2010-09-28 Uop Llc Process and apparatus for oligomerization in multiple stages with single fractionation column
US20080300439A1 (en) * 2005-11-17 2008-12-04 Snamprogetti S.P.A Process for the Separation of C5 Hydrocarbons Present in Streams Prevalently Containing C4 Products Used for the Production of Highoctane Hydrocarbon Compounds By the Se-Lective Dimerization of Isobutene
WO2007057151A3 (en) * 2005-11-17 2007-07-26 Snam Progetti Process for the separation of c5 hydrocarbons present in streams prevalently containing c4 products used for the production of high-octane hydrocarbon compounds by the se- lective dimerization of isobutene
US10618857B2 (en) 2005-11-17 2020-04-14 Saipem S.P.A. Process for the separation of C5 hydrocarbons present in streams prevalently containing C4 products used for the production of high-octane hydrocarbon compounds by the selective dimerization of isobutene
US8134039B2 (en) 2005-11-17 2012-03-13 Snamprogetti S.P.A. Process for the production of high-octane hydrocarbon compounds by the selective dimerization of isobutene contained in a stream which also contains C5 hydrocarbons
US20080242909A1 (en) * 2005-11-17 2008-10-02 Snamprogetti S.P.A. Process for the Production of High-Octane Hydrocarbon Compounds by the Selective Dimerization of Isobutene Contained in a Stream Which Also Contains C5 Hydrocarbons
WO2008085609A1 (en) * 2007-01-08 2008-07-17 Catalytic Distillation Technologies Treatment of olefin feed to paraffin alkylation
US20080164139A1 (en) * 2007-01-08 2008-07-10 Catalytic Distillation Technologies Treatment of olefin feed to paraffin alkylation
US7781634B2 (en) 2007-01-08 2010-08-24 Catalytic Distillation Technologies Treatment of olefin feed to paraffin alkylation
EA016950B1 (ru) * 2007-01-08 2012-08-30 Каталитик Дистиллейшн Текнолоджиз Обработка олефинового сырья для алкилирования парафинов
US8853483B2 (en) * 2008-12-02 2014-10-07 Catalytic Distillation Technologies Oligomerization process
US20100137668A1 (en) * 2008-12-02 2010-06-03 Catalytic Distillation Technologies Oligomerization process
EP2522424A1 (en) 2011-05-09 2012-11-14 King Abdulaziz City for Science and Technology Supported nanocatalyst for conversion of monoolefins, process for conversion of monoolefins and process for preparing the nanocatalyst
US20140012054A1 (en) * 2012-07-06 2014-01-09 Exxonmobil Chem Patents Inc Hydrocarbon Conversion Process
US20150126699A1 (en) * 2012-07-06 2015-05-07 Exxonmobil Chemical Patents Inc. Hydrocarbon Conversion Process
US9260357B2 (en) * 2012-07-06 2016-02-16 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion process
US9266791B2 (en) * 2012-07-06 2016-02-23 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion process

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IT1291729B1 (it) 1999-01-21
NL1009182A1 (nl) 1998-11-17
CA2235180C (en) 2006-08-15
ITMI971129A1 (it) 1998-11-15
GB9810558D0 (en) 1998-07-15
GB2325237A (en) 1998-11-18
NL1009182C2 (nl) 1999-05-19
AR009176A1 (es) 2000-03-08
CA2235180A1 (en) 1998-11-15
SA98190596B1 (ar) 2006-09-19
ITMI971129A0 (enrdf_load_stackoverflow) 1997-05-15

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